Rational Design of Functional Metal–Organic Frameworks as Chromatographic Stationary Phases: From Synthesis to Advanced Applications

Metal-organic frameworks (MOFs) have emerged as highly promising stationary phases in chromatographic separation technologies due to their exceptional structural tunability, high surface areas, and tailored pore environments. However, the transformation of these intrinsic advantages into practical chromatographic performance is often hindered by kinetic mass-transfer limitations, hydrolytic instability, and restricted accessibility for bulky analytes. This review systematically summarizes recent advances in the design and application of MOFs for chromatography, focusing on three critical material development directions: nano-sized MOFs, highly stable MOFs, and hierarchically porous MOFs. We first summarize the synthesis strategies, scientific challenges, and representative breakthroughs for each category, highlighting the transition between material properties and performance. The subsequent discussion critically evaluates their applications in gas chromatography (GC), liquid chromatography (HPLC), and capillary electrochromatography (CEC), with a particular focus on structure-performance relationships and the realization of material stability and nanoscale effects into enhanced separation efficiency, selectivity, and operational lifetime. By bridging the gap between advanced material synthesis and practical separation needs, this review aims to provide a roadmap for the development of next-generation and high-efficiency MOF-based stationary phases.